Method of making phenol-formaldehyde condensation products.



Unrrnn srarns PATENT onerou- J'AMES O. HANDY, OF PITTSBURGH, PENNSYLVANIA, ASSI'N U11, TO PITTSBURGH TEST- ING- LABORATORY, OF PITTSBURGH, PENNSYLVANIA, A CORPORATION OF PENN- SYLVANIA.

METHOD OF MAKING PHENOL-FORMALDEHYDE CONDENSATION PRODUCTS.

Specification of Letters Patent.

Patented Dec. 10, 1918.

No Drawing. Continuation of application Serial No. 2'00,710, fi1ed November 7, 1917. This application filed March 19, 1918. Serial No. 223,309.

' method of making such products for use in various industries, and of particular value as a cement or blnder for use in the brushmanufacturing industry.

It has heretofore been generally believed that products of this character produced without the use of a condensing agent were worthless, and although it has heretofore been proposed to make such products without the use of a condensing and catalytic agent, such proposals, in so far as I am aware, have been largely in the nature of impracticable suggestions to that eflect. So

far as I am aware, no practical commercial method has heretofore been disclosed by which this result could be accomplished.

I have, however, discovered that the use of condensing or catalytic agents may be entirely dispensed with in the commercial manufacture of these products. This is a decided advantage for a number of reasons. Condensing agents, even when used in the smallest amounts required for inducing a reaction, cause rapid heating, frothing, etc., rendering the reaction difficult to control and necessitating the use of very efiicient cooling devices for preventing loss of material, or rendering the apparatus employed useless because of solidification of the mate rial therein or because of the production therein of difficultly soluble matter.

Furthermore, it is not possible to make an anhydrous viscous liquid condensation product when a condensing agent is used, since separation by gravity will always leave some water in the viscous liquidproductand boiling oil water causes undesirable th1oken-, ing or solidification. p, j My meth0d. yieldS an anhydrous "l1qu1d product capable of binding bristles in brush manufacture and of otherwise serving as a bond or cement or a coating or impregnating material in the electric and other industries.

I have found that the following appear to be essential features in the making of useful products from phenols and formaldehydes without condensing agents, viz:

' 1. Theuse of commercial cresylic acid preferably of'97 to 99 per cent. strength and having a specific gravity approximating 1.03 at 20 'C., although an inferior reaction may be obtained with less pure cresylic acid.

2. The use of commercial 40 per cent. formaldehyde in ratios exceeding the one to one moliecular ratio of formaldehyde to cresylic acl 3 The boiling of .the mixture until the solids ih fliefirial'condensation product, de-

termined at 110 0., exceed 40 per cent. by 7 weight and are infusible, hard and tough, and also insoluble in acetone.

The initial boiling should 'be done without loss of material and the final boiling should be carried out in a manner to cause distillation of water and some of the formal-deboiled together without pressure, usually for about two hours. Water and excess formaldehyde are then distilled off and the temperature raised until about 120 C. is reached. The liquid is then quickly cooled gallons "may, however, be v a and is ready for use. .As above stated, the

boiling should take place until thesolid resin obtained by the evaporation of the viscous liquid, which separates from the watery reaction product, amountsto 40 per cent. or more by weight and is infusible, hardand tough and also insoluble in acetone.

This determination is made at a temperature is carried out Withou-tthe use of pressure a specific gravity of approximately 1.11 at either by relatively slow coolin after the final temperature is reached, or 1 y heatlng,

at any stage of the manufacture or use.

The liquid product obtained is anhydrous. It is 'a much more stable product than those made by theuse of catalytic agents. It has 20 0., and yields on drying at 110 0. from 40 to 50 er cent. of hard insoluble solid matter. ompositions'in which this liquid is used as a binder may be made with a tensile strength exceeding 1400- lbs. per square inch. It isespecially valuable for use in the brush-manufacturing industry,

but has many other uses eitheralone or mixed With solvents.

My invention is also applicable to the production of a solid or semi-solid product,

to a higher temperature,-or both, according to the nature ofthe product desired. For

example, after distillin off the Water and excess formaldehyde, with a final temperature of 120 0., a slow cooling will 've a product which, although clear and su stantially colorless, will not flow at ordinary temperatures. By carrying the final temperature to 140 0., I have produced aproduct in the form of a brittle resin which would soften slightly at 110 0.; and by carrying the final temperature to 160 0.,

the resinous product did not noticeably soften at 110 .0. These temperatures are illustrative only. The rate of coolin' of the product may be regulated in any we known manner. For instance, 'if the cooling is carried out in a water-jacketed vessel, the

clrculation of cooling water in the jacket may be retarded or entirely stopped and the heated material allowed to stand surrounded-whan 10 0. and not more than 120 0..

by water which will cool slowly to room temperature as the mass of material gives up its'heat slowly by conduction.

The present application is a continuation of my application serial No. 200,710, filed November 7, 1917. f

I claim:

' 1. The method of making, without the use of a condensingagent, a phenol-formaldehyde 'condensat1on product in ,the form of an anhydrous liquid which consists in boiling a mixture composed of commercial cresylic acid or from 97 to 99 per cent. strength and commercial 40 per centformaldehyde, until the solidsin the condense tron product determined at 110 0., ual or exceed 40 per cent. by weight,- the nal boiling. during which. water and excess 1 formaldehyde are distilled off being at a temperature above 100 0.

2. The method of making, without the equal or exceed tO 'per cent. by Weight, the

final boiling during which water and excess formaldehyde are distilled off being at a' temperature of from 110 to 120 0.-

3. The herein. described method of making, without theuse of a condensing agent, a phenol-formaldehyde condensation prod uct, which consists in boiling a mixture composed of commercial cresylic acid of from 97 to 99 per cent. strength and commercial 40 per cent. formaldehyde, the two being mixed in ratios exceeding the one to one molecular ratio of formaldehyde to cresylic acid, boiling the mixture until the solids in the condensation product, determined at 110 0., equal or exceed 40 per cent. by weight and are infusible, hard and tough, and also insoluble in acetone, the

/' final boiling during'whichWaterand excess formaldehyde are distilled off being at a temperature not less than 110 0. or more than 120 .0. y

' 4. The herein described method of forming, without the use of a condensing agent, a phenol-formaldehyde condensation rodnot in the form of an anh drous vlscous termined at 0., .equal or exceed 40 er.

cent. by weight, the final boilin 7 during which water and exgess/formalde yde are distilled ofl ingit a temperature of not 5. The herein described method of making a phenol-condensation product without the use of a condensing agent, which consists in boilin .a mixture composed of commercial cresyhc. acid and formaldehyde mixed in ratios exceedin the one to one molecular ratioof forma dehyde to cresylic acid, and boiling the mixture until the solids in the condensation. product equal or exceed 40 per cent.'by'weight, determined at 110 0., the

final boiling during which water and excess formaldehyde are distilled'ofi being at a temperature in excess of 100 0.

"'6. The herein described method of making a phenol-condensation product without the use of'a. condensing agent, which consists in boiling a mixture composed of commercial 

